EP3545025A1 - Procédé pour fabriquer un objet au moins en partie recouvert - Google Patents

Procédé pour fabriquer un objet au moins en partie recouvert

Info

Publication number
EP3545025A1
EP3545025A1 EP17809230.0A EP17809230A EP3545025A1 EP 3545025 A1 EP3545025 A1 EP 3545025A1 EP 17809230 A EP17809230 A EP 17809230A EP 3545025 A1 EP3545025 A1 EP 3545025A1
Authority
EP
European Patent Office
Prior art keywords
article
compounds
groups
acid
isocyanate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP17809230.0A
Other languages
German (de)
English (en)
Other versions
EP3545025B1 (fr
Inventor
Dirk Achten
Thomas BÜSGEN
Thomas Michaelis
Roland Wagner
Bettina METTMANN
Levent AKBAS
Jürgen Hättig
Arnaud GUEDOU
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Deutschland AG
Original Assignee
Covestro Deutschland AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Covestro Deutschland AG filed Critical Covestro Deutschland AG
Publication of EP3545025A1 publication Critical patent/EP3545025A1/fr
Application granted granted Critical
Publication of EP3545025B1 publication Critical patent/EP3545025B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
    • B29C71/0009—After-treatment of articles without altering their shape; Apparatus therefor using liquids, e.g. solvents, swelling agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/118—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using filamentary material being melted, e.g. fused deposition modelling [FDM]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
    • B33Y40/20—Post-treatment, e.g. curing, coating or polishing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0828—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing sulfonate groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/282—Alkanols, cycloalkanols or arylalkanols including terpenealcohols
    • C08G18/2825—Alkanols, cycloalkanols or arylalkanols including terpenealcohols having at least 6 carbon atoms
    • C—CHEMISTRY; METALLURGY
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    • C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
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    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3228—Polyamines acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3234—Polyamines cycloaliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
    • C08G18/3857—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur having nitrogen in addition to sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/44—Polycarbonates
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/4808—Mixtures of two or more polyetherdiols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
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    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
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    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/08—Polyurethanes from polyethers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/141—Processes of additive manufacturing using only solid materials
    • B29C64/153—Processes of additive manufacturing using only solid materials using layers of powder being selectively joined, e.g. by selective laser sintering or melting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2433/10—Homopolymers or copolymers of methacrylic acid esters

Definitions

  • the present invention relates to a method for producing an at least partially coated article, comprising the step of producing the article by means of an additive manufacturing method from a building material, wherein the building material comprises a thermoplastic polyurethane material.
  • the invention further relates to an at least partially coated article obtained by a method according to the invention.
  • the additive manufacturing processes are also referred to as "3D printing.”
  • the starting material for the articles to be produced in a 3-D printing process can be polyamides or thermoplastic polyurethane
  • a 3-D printing method has the disadvantage that the surface of the objects is porous and therefore subject to increased wear and tear, while dirt adheres relatively easily to the surface due to the porous surface structure, which can significantly affect the aesthetics of the article
  • the objects may absorb water or moisture, which may adversely affect the structure and / or the stability of the objects
  • it is known in the art to grind and / or polish the surface of the plastic articles it is known in the art to grind and / or polish the surface of the plastic articles.
  • the surface of the plastic objects may indeed be made smoother.
  • a substantial removal of the pores is possible only with considerable effort, so that it is usually not guaranteed even after polishing that no dirt adheres to the surface.
  • polishing the surface is not always possible. Because polishing removes material from the surface, the geometry of the article can be changed, which in some cases is undesirable. In addition, even by polishing the surface can not be guaranteed that it is fluid-repellent, especially water-repellent, as well as waterproof. However, depending on the material used in the manufacture of such plastic articles, it is desired that the surface be water repellent or waterproof.
  • WO 2016/030490 Al discloses a method for impregnating molded parts produced in a 3 D printing process, in particular of powder-based production or printing processes, with a liquid and / or sprayable impregnating agent, wherein Impregnating agent 25 to 95 wt .-% of a solvent or solvent mixture and added to 100 wt .-% of supplemented in the solvent or solvent mixture dissolvable plastic or plastic mixture, each based on the total composition of the impregnating agent, and wherein the impregnating agent on the surface to be impregnated is applied to the molding and dried after the application of the impregnating agent, the impregnated surface.
  • Impregnating agent 25 to 95 wt .-% of a solvent or solvent mixture and added to 100 wt .-% of supplemented in the solvent or solvent mixture dissolvable plastic or plastic mixture, each based on the total composition of the impregnating agent, and wherein the impregnating agent on the surface to be impregnated
  • An object of the present invention is to overcome at least one disadvantage of the prior art at least in part. Furthermore, the present invention has the object to provide an integrated additive manufacturing process, with which the feel of the manufactured article is improved with improved adhesion of its coating. Furthermore, it was an object of the invention to be able to produce an article as cost-effectively as possible and / or individualized and / or resource-conserving.
  • the object is achieved by a method according to claim 1.
  • E in an inventive method obtained, at least partially coated article is mentioned in claim 15.
  • Advantageous further education are given in the dependent claims. They can be combined as desired, provided the context does not clearly result in the opposite.
  • a method for producing an at least partially coated article comprising the step of producing the article by means of an additive manufacturing method from a building material, wherein the building material comprises a thermoplastic polyurethane material, characterized in that the method after the manufacture of the article further Step includes: at least partially contacting the article with a preparation selected from: aqueous polyurethane dispersion, aqueous dispersion of an OH group-containing polymer, said dispersion further containing an NCO group-containing compound, aqueous preparation of an NCO group-containing compound, wherein this preparation does not contain OH-G-containing polymers or a combination of at least two thereof.
  • a combination of at least two of the stated preparations is understood as meaning both a mixture of at least two of the dispersions mentioned or aqueous preparations and a sequence of contacting the article with the various selected preparations.
  • the additive manufacturing process can be selected from fused filament fabrication (FFF or Fused Deposition Modeling, FDM), ink jet printing, photopolymer jetting, selective laser sintering, selective laser melting, binder jetting based additive manufacturing, multijet fusion based Additive Manufacturing, High Speed Sintering Process and Laminated Object Modeling.
  • FFF fused filament fabrication
  • FDM Fused Deposition Modeling
  • the additive manufacturing process is a sintering process.
  • Sintering processes in the context of the present invention are processes which use, in particular, thermoplastic powders to build up articles in layers.
  • thin powder layers are applied via a so-called coater and then selectively melted by means of an energy source.
  • the surrounding powder supports the component geometry. Complex geometries are thus more economical to manufacture than in the FDM process.
  • various items can be packed or made tightly packed in the so-called powder bed.
  • powder-based additive manufacturing processes are among the most economical additive manufacturing processes on the market. They are therefore used predominantly by industrial users. Examples of powder-based additive manufacturing processes are the so-called laser sintering (SLS, Selective Laser Sintering) or high-speed sintering (HSS).
  • thermoplastic polyurethane material is preferably elastic, that is, it exhibits an elongation at break in the tensile test according to DIN 53504 of> 50%.
  • the material may have, for example, a compression set after 25% compression (DIN 53517) of absolutely ⁇ 10%.
  • the thermoplastic polyurethane material may contain other additives such as fillers, stabilizers and the like, but also other polymers.
  • the total content of additives in the elastic polymer can be, for example,> 0.1% by weight to ⁇ 70% by weight, preferably> 1% by weight to ⁇ 30% by weight.
  • the article is at least partially contacted with a preparation after its production.
  • the contacting can be carried out by immersion, brushing, spraying or other known application methods for aqueous dispersions. Drying of the article after the contacting step can be carried out, for example, at room temperature (20 ° C.), at elevated temperature and optionally with vacuum assistance. By drying, the water of the preparation is removed. Preferably, the preparation is free of organic solvents.
  • the preparation may be an aqueous polyurethane dispersion. In these, particles of a polyurethane polymer are dispersed in an aqueous phase. Such dispersions are also referred to as one-component or 1K dispersions.
  • a coalescence of the particles and thus a film formation can take place.
  • aqueous polyurethane dispersions can be used. However, preference is given to anionically hydrophilicized and anionic / nonionically hydrophilicized polyurethane dispersions.
  • the preparation may further be an aqueous dispersion of an OH-containing polymer, which dispersion also contains an NCO-containing compound.
  • Such preparations are also referred to as two-component or 2K dispersions.
  • a reaction takes place between the polymer and the NCO-containing compound, whereby a cured polymer film can be obtained in the dried state.
  • the compound having NCO groups can be, for example, an optionally hydrophilicized diisocyanate, triisocyanate or an at least difunctional, NCO-terminated prepolymer. It is also possible for the preparation to be an aqueous preparation of an NCO-group-containing compound, this preparation not containing OH-containing polymers.
  • Such a preparation may also be referred to as an aqueous preparation of a hydrophilized isocyanate, which, unlike a 2K polyurethane dispersion, lacks the polymer component for reaction with the NCO groups.
  • a hydrophilized isocyanate reacts with reactants on the surface of the building material.
  • Such preparations are used, inter alia, as crosslinking components for water-dilutable two-component polyurethane coatings (2K PU paints). Examples of these are nonionic, with the aid of polyethers hydrophilic-modifi ed polyisocyanates.
  • polyether-modified water-soluble polyisocyanates which additionally have ionic groups, for example sulfonate groups or amino or ammonium groups, for improving the emulsifiability or for achieving special effects.
  • the preparation may contain other additives. In particular, it may be silicone-containing, surface-active additives.
  • the use of said preparations or combinations thereof avoids the problems associated with organic solvents.
  • the material derived from the preparation and the material of the article are each polyurethanes or isocyanates, so that good compatibility can be expected. Then the adhesion of the coating is better than with less chemically related materials.
  • a polyurethane film adhering to the article improves the haptic feel that the article triggers, not only by smoothing out unevenness in the surface of the article.
  • Loose particles adhering to the surface which may still be present in particular after powder sintering processes, are bound into the film layer and thus fixed.
  • those excipients which are used in sintering powders to improve the flow and absorption properties such as Ti0 2 , carbon black or S1O 2 are fixed. This can avoid difficulties associated with their use. Examples include dusting or chalking of the surface and possible skin irritation caused by loose particles. It can be obtained velvety, non-chalking surfaces for the object. Possibly present pores in the article are at least partially filled.
  • a polyurethane film adhered to the article can also accommodate at least a portion of the mechanical forces, in particular tensile forces, applied to the article and thereby increase it Strength of the article can contribute.
  • the article in the areas contacted by the polyurethane dispersion can increase the toughness and / or the hardness, for example by> 2 or> 5 Shore A degrees of hardness and / or increase the modulus of elasticity by> 5 %, preferably> 10%.
  • the abrasion resistance of these areas can be increased.
  • the process according to the invention also makes it possible to increase the density of the processed building material by, for example,> 5% or> 10% in the areas contacted by the preparation after the dispersion has dried.
  • the aqueous polyurethane dispersion is anionically and / or nonionically hyrophilized.
  • the aqueous polyurethane dispersions are preferably hydrophilized anionically by means of sulfonate groups and / or carboxylate groups. Particular preference is given to anionic hydrophilicization exclusively containing sulfonate groups.
  • the aqueous polyurethane dispersion is obtainable by A) isocyanate-functional prepolymers of Al) organic polyisocyanates
  • polymeric polyols having number average molecular weights of 400 to 8000 g / mol, preferably from 400 to 6000 g / mol and more preferably from 600 to 3000 g / mol, and OH functionalities from 1, 5 to 6, preferably from 1, 8 to 3, more preferably from 1.9 to 2.1, and
  • B l optionally with amino-functional compounds having molecular weights of 32 to 400 g / mol and B2) are reacted with amino-functional, anionic or potentially anionic hydrophilicizing agents with chain extension and the prepolymers before, during or after step B) are dispensed in water disp.
  • Isocyanate-reactive groups are, for example, primary and secondary amino groups, hydroxyl groups or thiol groups.
  • polyurethane dispersions more preferably have less than 5% by weight, more preferably less than 0.2% by weight, based on the total dispersions, of unbound organic amines or of ammonia. If desired, the prepolymer A) before, during or after the dispersion by admixture of a base can be converted completely or partially into the anionic form.
  • hydrophilicizing agents In order to achieve anionic hydrophilization, hydrophilicizing agents must be used in A4) and / or B2) which have at least one NCO-reactive group, such as amino, hydroxy or thiol groups, and moreover COO. SO-. ' or PO-. as anionic or their fully or partially protonated acid forms as potentially anionic groups.
  • Suitable polyisocyanates of component AI) are the aliphatic, aromatic or cycloaliphatic polyisocyanates of an NCO functionality greater than or equal to 2 which are known per se to the person skilled in the art.
  • polyisocyanates examples include 1, 4-butylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate (HI), isophorone diisocyanate (iPDI), 2,2,4- and / or 2,4,4-trimethylhexamethylene diisocyanate, which are isomeric Bis- (4,4'-isocyanatocyclohexyl) methanes or mixtures thereof any isomer content, 1, 4-cyclohexylene diisocyanate, 4-isocyanatomethyl-l, 8-octane diisocyanate (Nonantriiso cyanat), 1, 4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate, 1, 5-Naphthylendiisoeyanat, 2,2 '- and / or 2,4' and / or 4,4'-diphenylmethane diisocyanate, 1,3- and
  • polyisocyanates or polyisocyanate mixtures of the abovementioned type having exclusively aliphatically or cycloaliphatically bonded isocyanate groups or mixtures of these and an average NCO functionality of the mixture of from 2 to 4, preferably from 2 to 2.6 and particularly preferably from 2 to 2 ; 4.
  • the impregnated 3D printed polyurethanes can additionally be protected against weathering and yellowing.
  • AI isomeric bis (4,4'-isocyanatocyclohexyl) methanes and mixtures of the abovementioned diisocyanates.
  • polymeric polyols having a number average molecular weight Mn of from 400 to 8000 g / mol, preferably from 400 to 6000 g / mol and more preferably from 600 to 3000 g / mol, are used. These preferably have an OH functionality of from 1.5 to 6, particularly preferably from 1.8 to 3, very particularly preferably from 1.9 to 2.1.
  • Such polymeric polyols are the polyester polyols known in polyurethane lacquer technology, polyacrylate polyols, polyurethane polyols, polycarbonate polyols, polyether polyols, polyester polyacrylate polyols, polyurethane polyacrylate polyols, polyurethane polyester polyols, polyurethane polyether polyols, polyurethane polycarbonate polyols and polyester polycarbonate polyols. These can be used in A2) individually or in any mixtures with each other.
  • these available polyurethanes may also contain unsaturated double bonds, which are accessible to a subsequent radical crosslinking reaction.
  • monohydroxy-functional (meth) acrylate-containing alcohols are 2-hydroxyethyl (meth) acrylate, caprolactone-extended modifications of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth ) acrylate, 3-hydroxy-2,2-dimethylpropyl (meth) acrylate, the average monohydroxyfunktionelle di-.
  • Tri or penta (meth) acrylates of polyhydric alcohols such as methylmethylolpropane, glycerol, pentaerythritol, ditrimethylolpropane, dipentaerythritol, ethoxylated, propoxylated or alkoxylated trimethylolpropane, glycerol, pentaerythritol, ditrimethylolpropane, dipentaerythritol or technical mixtures thereof.
  • Suitable polyester polyols are also the known polycondensates of di- and optionally tri- and tetraols and di- and optionally tri- and tetracarboxylic acids or hydroxy carboxylic acids or lactones. Instead of the free polycarboxylic acids, it is also possible to use the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols for the preparation of the polyesters.
  • diols examples include ethylene glycol, butylene glycol, diethylene glycol, triethylene glycol, polyalkyl englycols such as polyethylene glycol, furthermore 1,2-propanediol, 1,3-propanediol, butanediol (1,3), butanediol (1,4), hexanediol (I, 6) and isomers, neopentyl glycol or hydroxypivalic acid neopentyl glycol esters, with hexanediol (1,6) and isomers, butanediol (1,4), neopentyl glycol and neopentyl glycol hydroxypivalate being preferred.
  • polyalkyl englycols such as polyethylene glycol, furthermore 1,2-propanediol, 1,3-propanediol, butanediol (1,3), butanediol (1,4),
  • polyols such as trimethylolpropane, glycerol, erythritol, pentaerythritol, trimethylolbenzene or trishydroxyethyl isocyanurate.
  • dicarboxylic acids phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid,
  • Cyclohexanedicarboxylic acid, adipic acid, azelaic acid, sebacic acid, glutaric acid, tetrachlorophthalic acid, maleic acid, fumaric acid, itaconic acid, malonic acid, suberic acid, 2-methyl succinic acid, 3,3-diethylglutaric acid and / or 2,2-dimethyl succinic acid can be used.
  • the acid source used may also be the corresponding anhydrides.
  • the average functionality of the polyol to be esterified is greater than 2, it is additionally possible to use monocarboxylic acids such as benzoic acid and hexanecarboxylic acid.
  • Preferred acids are aliphatic or aromatic acids of the abovementioned type. Particular preference is given to adipic acid, isophthalic acid and phthalic acid.
  • Hydroxycarboxylic acids which can be used as reactants in the preparation of a polyester polyol having terminal hydroxyl groups are, for example, hydroxycaproic acid, hydroxybutyric acid, hydroxydecanoic acid, hydroxystearic acid and the like.
  • Suitable lactones are caprolactone, butyrolactone and homologs. Preference is given to caprolactone.
  • hydroxyl-containing polycarbonates preferably polycarbonatediols, having number-average molecular weights Mn of from 400 to 8000 g / mol, preferably from 600 to 3000 g / mol.
  • carbonic acid derivatives such as diphenyl carbonate, dimethyl carbonate or phosgene
  • diols examples include ethylene glycol, 1,2- and 1,3-propanediol, 1,3- and 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, 1,4-bishydroxymethylcyclohexane, 2- Methyl-l, 3-propanediol, 2,2,4-Trimethylpentandiol-l, 3, dipropyl glycol, polypropylene glycols, dibutyl englykol, polybutylene glycols, bisphenol A and lactonmodifi ed diols of the above mentioned type.
  • the diol component preferably contains from 40 to 100% by weight of hexanediol, particular preference being given to 1,6-hexanediol and / or hexanediol derivatives.
  • hexanediol derivatives are based on hexanediol and have ester or ether groups in addition to terminal OH groups.
  • Such derivatives are obtainable by reaction of hexanediol with excess caprolactone or by etherification of hexanediol with itself to di- or trihexylenglykol.
  • Hy droxylgrupp en having polycarbonates are preferably constructed linearly.
  • polyether polyols can be used. Suitable examples are the polytetramethylene glycol polyethers known per se in polyurethane chemistry, such as are obtainable by polymerization of tetrahydrofuran by means of cationic ring opening.
  • polyether polyols are the per se known addition products of styrene oxide, ethylene oxide, propylene oxide, butylene oxide and / or epichlorohydrin to di- or polyfunctional starter molecules.
  • Polyether polyols, based on the at least proportional addition of ethylene oxide to di- or polyfunctional starter molecules, can also be used as component A4) (nonionic hydrophilicizing agents).
  • starter molecules it is possible to use all compounds known from the prior art, for example water, butyl diglycol, glycerol, diethylene glycol, trimethylolpropane, propylene glycol, sorbitol, ethylenediamine, triethanolamine, 1,4-butanediol.
  • Preferred components in A2) are polytetramethylene glycol polyethers and polycarbonate polyols or mixtures thereof, and polytetramethylene glycol polyethers are particularly preferred.
  • polyols of the stated molecular weight range having up to 20 carbon atoms such as ethylene glycol, diethylene glycol, trimethyl glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 3-butylglycol, cyclohexanediol, 1,4-cyclohexanedimethanol, 1,6-hexanediol, neopentyl glycol, hydroquinone dihydroxyethyl ether, bisphenol A (2,2-bis (4-hydroxyphenyl) propane), hydrogenated bisphenol A (2,2-bis (4-hydroxycyclohexyl) propane ), Trimethylolpropane, trimethylolethane, glycerol, pentaerythritol and any mixtures thereof.
  • ester diols of the stated molecular weight range, such as ⁇ -hydroxybutyl ⁇ -hydroxycaproic acid ester, ⁇ -hydroxyhexyl- ⁇ -hydroxybutyric acid ester, adipic acid ( ⁇ -hydroxyethyl) ester or terephthalic acid bis ( ⁇ -hydroxyethyl) ester.
  • monofunctional isocyanate-reactive hydroxyl group-containing compounds can also be used in A3). Examples of such monofunctional compounds are ethanol, n-butanol, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether,
  • Tripropylene glycol monobutyl ether 2-ethylhexanol, 1-octanol, 1-dodecanol, 1-hexadecanol.
  • Suitable ionically or potentially ionically hydrophilic compounds are e.g. Mono- and dihydroxycarboxylic acids, mono- and dihydroxysulphonic acids, and mono- and dihydroxyphosphonic acids and their salts, such as dimethylolpropionic acid, dimethylolbutyric acid, hydroxypivalic acid, malic acid, citric acid, glycolic acid, lactic acid, the propoxylated adduct of 2-butenediol and NaHSC, e.g. described in DE-A 2 446 440 (page 5-9, formula l-l l l).
  • Suitable nonionically hydrophilicizing compounds of component A4) are e.g. Polyoxyalkylene ethers containing at least one hydroxyl, amino or thiol group. Examples are the monohydroxy-functional, on average 5 to 70, preferably 7 to 55 ethylene oxide units per molecule having Polyalkylenoxidpolyetheralkohole, as they are accessible in a conventional manner by alkoxylation of suitable starter molecules (eg in Ullmann's Encyclopaedia of Industrial Chemistry, 4th Edition, Volume 19 , Verlag Chemie, Weinheim p. 31-38). These are either pure polyethylene oxide ethers or mixed polyalkylene oxide ethers, wherein they contain at least 30 mol%, preferably at least 40 mol% based on all alkylene oxide units contained in ethylene oxide units.
  • nonionic compounds are monofunctional mixed polyalkylene oxide polyethers having from 40 to 100 mole% of ethylenoxide and from 0 to 60 mole% of propyl enoxide units.
  • Suitable starter molecules for such nonionic hydrophilicizing agents are saturated monoalcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, the isomeric pentanols, hexanols, octanols and nonanols, n-decanol, n-dodecanol, n-butanol.
  • monoalcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, the isomeric pentanols, hexanols, octanols and nonanols, n-decanol, n-dodecanol, n-butanol.
  • Alkylene oxides which are suitable for the alkoxylation reaction are, in particular, ethylene oxide and propylene oxide, which can be used in any desired order or even as a mixture in the alkoxylation reaction.
  • organic di- or polyamines such as, for example, 1,2-ethylenediamine, 1,2- and 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, isophoronediamine, isomer mixture of 2,2,4- and 2,4,4-trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethylenetriamine, 4,4-diaminodicyclohexylmethane, hydrazine hydrate, and / or dimethylethylenediamine.
  • 1,2-ethylenediamine 1,2- and 1,3-diaminopropane
  • 1,4-diaminobutane 1,6-diaminohexane
  • isophoronediamine isomer mixture of 2,2,4- and 2,4,4-trimethylhexamethylenediamine
  • 2-methylpentamethylenediamine diethylenetriamine
  • component Bl compounds which, in addition to a primary amino group, also have secondary amino groups or, in addition to an amino group (primary or secondary), also OH groups, can be used.
  • primary secondary amines such as diethanolamine, 3-amino-1-methylaminopropane, 3-amino-1-ethylaminopropane, 3-amino-1-cyclohexylaminopropane, 3-amino-1-methylaminobutane,
  • Alkanolamines such as N-aminoethylethanolamine, ethanolamine, 3-aminopropanol, Neop entanolamin.
  • component Bl) and monofunctional isocyanate-reactive amine compounds are used, such as methylamine, ethylamine, propylamine, butylamine, octylamine, laurylamine, stearylamine, isononyloxypropylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, N-methylaminopropylamine, diethyl (methyl) aminopropylamine, morpholine , Piperidine, or suitable substituted derivatives thereof, amide amines of diprimary amines and monocarboxylic acids, monocrimets of diprimary amines, primary / tertiary amines, such as N, N-dimethylaminopropylamine.
  • Suitable anionically hydrophilicizing compounds of component B2) are alkali metal salts of mono- and diaminosulfonic acids.
  • anionic hydrophilicizing agents are salts of 2- (2-aminoethylamino) ethanesulfonic acid, ethylenediamine propyl or butylsulfonic acid, 1,2- or 1,3-propylenediamine- ⁇ -ethylsulfonic acid or taurine.
  • the salt of cyclohexylaminopropanesulfonic acid (CAPS) from WO-A 01/88006 as anionic Hydrophilizing agents are used.
  • anionic hydrophilicizing agents B2 are those which contain sulfonate groups as ionic groups and two amino groups, such as the salts of 2- (2-aminoethylamino) ethylsulfonic acid and 1, 3-propylenediamine- ⁇ -ethylsulfonic acid.
  • sulfonate groups as ionic groups and two amino groups, such as the salts of 2- (2-aminoethylamino) ethylsulfonic acid and 1, 3-propylenediamine- ⁇ -ethylsulfonic acid.
  • the components Al) to A4) and B l) to B2) are used in the following amounts, the individual amounts always adding up to 100% by weight: 5 to 40% by weight. -% component AI),
  • the components Al) to A4) and Bl) to B2) are used in the following amounts, the individual amounts always adding up to 100% by weight:
  • the components Al) to A4) and Bl) to B2) are used in the following amounts, the individual amounts always adding up to 100% by weight:
  • the preparation of the polyurethane dispersions can be carried out in one or more stages in homogeneous or multistage reaction, partly in disperse phase. After complete or partial polyaddition from Al) to A4), a dispersing, emulsifying or dissolving step takes place. This is followed, if appropriate, by a further polyaddition or modification in disperse phase.
  • the constituents A2) to A4) and the polyisocyanate component AI) are usually completely or partially initially charged for preparation of a polyurethane prepolymer which is soocyanate-functional and, if appropriate, diluted with a water-miscible but isocyanate-inert solvent and heated to temperatures in the range of 50 to 120 ° C.
  • the catalysts known in polyurethane chemistry can be used.
  • Suitable solvents are the customary aliphatic, ketofunctional solvents such as acetone, 2-butanone, which may be added not only at the beginning of the preparation but optionally also in parts later. Preference is given to acetone and 2-butanone, particular preference to acetone. The addition of other solvents without isocyanate-reactive groups is possible, but not preferred.
  • the components of Al) to A4) which are optionally not added at the beginning of the reaction, are metered in.
  • the molar ratio of isocyanate groups to isocyanate-reactive groups is generally 1.05 to 3.5, preferably 1.1 to 3.0, particularly preferably 1.1 to 2, 5th
  • the reaction of components AI) to A4) to the prepolymer takes place partially or completely, but preferably completely.
  • polyurethane prepolymers containing free isocyanate groups are obtained in bulk or in solution.
  • the resulting prepolymer with the aid of aliphatic ketones such as acetone or 2-butanone dissolved.
  • the reaction of components AI) to A4) to the prepolymer takes place partially or completely, but preferably completely.
  • polyurethane prepolymers which contain free cyanoacrylate groups are obtained in bulk or in solution.
  • bases such as tertiary amines, for example trialkylamines having 1 to 12, preferably 1 to 6, C atoms in each alkyl radical or alkali metal bases such as the corresponding hydroxides are used.
  • alkyl radicals may, for example, also carry hydroxyl groups, as in the case of the dialkylmonoalkanol, alkyldialkanol and trialkanolamines.
  • Suitable neutralizing agents are also inorganic bases, such as aqueous sodium, lithium or potassium hydroxide.
  • sodium hydroxide, lithium hydroxide or potassium hydroxide Preference is given to sodium hydroxide, lithium hydroxide or potassium hydroxide, particular preference to sodium hydroxide, lithium hydroxide or potassium hydroxide.
  • the sodium, lithium or potassium ions are already bound as a cation to anionically functionalized building blocks.
  • the molar amount of the bases is generally 50 and 125 mol%, preferably between 70 and 100 mol% of the molar amount of the acid groups to be neutralized.
  • the neutralization can also take place simultaneously with the dispersion in which the dispersing water already contains the neutralizing agent.
  • Suitable components for chain extension are organic di- or polyamines B1) such as, for example, ethylenediamine, 1,2- and 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, isophoronediamine, mixture of 2,2,4- and isomers 2,4,4-trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethylenetriamine, diaminodicyclohexylmethane and / or dimethyl ethylenediamine.
  • organic di- or polyamines B1 such as, for example, ethylenediamine, 1,2- and 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, isophoronediamine, mixture of 2,2,4- and isomers 2,4,4-trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethylenetriamine, diaminodic
  • compounds B1) which, in addition to a primary amino group, also have secondary amino groups or, in addition to an amino group (primary or secondary), also OH groups.
  • primary secondary amines such as Diethanolamine, 3-amino-1-methylaminopropane, 3-amino-1-ethylaminopropane, 3-amino-1-cyclohexylaminopropane, 3-amino-1-methylaminobutane, alkanolamines such as - aminoethylethanolamine, ethanolamine, 3-aminopropanol, neopentanolamine for chain extension or Termination be used.
  • amines B l with an isocyanate-reactive group such as methylamine, ethylamine, propylamine, butylamine, octylamine, laurylamine, stearylamine, isononyloxypropylamine, dim ethylamine, diethylamine, dipropylamine, dibutylamine, N-methylaminopropylamine, diethyl (methyl) aminopropylamine , Morpholine, piperidine, or suitable substituted derivatives thereof, amide amines from diprimary amines and monocarboxylic acids, monocrimets of diprimary amines, primary / tertiary amines, such as N, N-dimethylaminopropylamine.
  • anionic hydrophilicizing agents according to the definition B2) with M; or NH groups are used for the chain extension, the chain extension of the prepolymers is preferably carried out before the dispersion.
  • the degree of chain extension ie the equivalent ratio of NCO-reactive groups of the compounds used for chain extension and chain termination to free NCO groups of the prepolymer, is generally between 40 and 150%, preferably between 50 and 120%, particularly preferably between 60 and 120%.
  • the aminic components B l) and B2) may optionally be used in diluted form in the process according to the invention individually or in mixtures, wherein in principle any order of addition is possible.
  • the diluent content in the chain-extending component used in B) is preferably 40 to 95% by weight.
  • the dispersion preferably takes place after the chain extension.
  • the dissolved and chain extended polyurethane polymer is optionally sheared under high shear, e.g. vigorous stirring, either added to the dispersing water or, conversely, the dispersing water is stirred into the chain-extended polyurethane polymer solutions. It is preferred to add what it contains into the dissolved chain-extended polyurethane polymer.
  • the residual content of organic solvents in the polyurethane dispersions is typically less than 2% by weight, preferably less than 1% by weight, based on the total dispersion.
  • the pH of the polyurethane dispersions is typically less than 8.0, preferably less than 7.5 and more preferably between 5.5 and 7.5.
  • the polyurethane dispersions contain at least 10% by weight of polyurethane, based on the solids content of all film-forming polymers contained in the dispersion.
  • polyurethane is not used exclusively as the film-forming polymer, it is also possible to use other polymer dispersions, e.g. based on polyesters, poly (meth) acrylates, polyepoxides, polyvinyl acetates, polyethylene, polystyrene, polybutadienes, polyvinyl chloride and / or corresponding copolymers.
  • the polyurethane dispersions may additionally contain auxiliaries and additives. Examples of such auxiliaries and additives are crosslinkers, thickeners, thixotropic agents, stabilizers, antioxidants, light stabilizers, emulsifiers, surfactants, plasticizers, pigments, fillers and leveling agents.
  • the number-average particle size of the particles in the aqueous polyurethane dispersion determined by means of laser correlation spectroscopy is less than 1000 nm, preferably less than 500 nm. Such particle sizes can bring about good sedimentation stability of the dispersions.
  • the aqueous polyurethane dispersion solids contents of 10 to 70 wt .-%, particularly preferably from 30 to 70% by weight, most preferably from 30 to 65% by weight based on the polyurethane contained therein ,
  • the aqueous dispersion of an OH-containing polymer which also contains an NCO-containing compound comprises the components:
  • G optionally urethanization catalysts, and optionally further auxiliaries and additives.
  • Suitable as component A) are the hydroxyl-containing polyepoxy (meth) acrylates known per se with an OH number in the range from 20 to 300 mg KOH / g, preferably from 100 to 280 mg KOH / g, more preferably from 150 to 250 mg KOH /'G.
  • Aromatic, hydroxy group-containing polyepoxy (meth) acrylates based on reaction products of acrylic acid and / or methacrylic acid with aromatic glycidyl ethers (epoxides) are preferably used, particularly preferably aromatic glycidyl ethers of monomeric, oligomeric or polymeric bisphenol A and / or bisphenol F or their alkoxylated derivatives.
  • the listed under component A) compounds can be used alone or in mixtures.
  • Component B) comprises compounds different from component A) with at least one isocyanate-reactive group and at least one radiation-curable double bond.
  • Component B) preferably contains monohydroxy-functional, (meth) acrylate-containing alcohols.
  • Such monohydroxy-functional, (meth) acrylate-containing alcohols are, for example, 2-hydroxyethyl (meth) acrylate, caprolactone-extended modifications of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4 Hydroxybutyl (meth) acrylate, 3-hydroxy-2,2-dimethylpropyl (meth) acrylate, containing on average monohydroxy-functional di-, tri- or penta (meth) acrylates of polyhydric alcohols, such as trimethylolpropane, glycerol, pentaerythritol, ditrimethylolpropane, dipentaerythritol, ethoxylated, propoxylated
  • Particularly preferred monohydroxy-functional (meth) acrylate-containing alcohols are 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, pentaerythritol triacrylate,
  • alcohols which can be obtained from the reaction of double-bond-containing acids with optionally double-bond-containing, monomeric epoxide compounds can also be used as component (B) as monohydroxy-functional, (meth) acrylate-containing alcohols.
  • component B) may contain hydroxyl groups and unsaturated group-containing oligomers and polymers. Preference is given to polyester (meth) acrylates.
  • polyester (meth) acrylates the hydroxyl-containing polyester (meth) acrylates having an OH number in the range from 15 to 300 mg KOH / g substance, particularly preferably from 60 to 200 mg KOH / g substance, are preferably used as component B).
  • polyester (meth) acrylates are preferred by reacting bl) polyfunctional alcohols of from 62 to 320 g / mol with b2) dicarboxylic acids and also b3) acrylic acid, methacrylic acid and / or dimeric acrylic acid.
  • bl Particularly preferred for bl) are di-, tri- and tetra-functional alcohols such as butanediol, pentanediol, 1,6-hexanediol, neopentyl glycol, cyclohexanediol, 1,4-cyclohexanedimethanol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, glycerol, Trimethylolpropane and pentaerythritol. As well as the reaction product of 1 mole of trimethylolpropane with 4 moles of ethylene oxide.
  • di-, tri- and tetra-functional alcohols such as butanediol, pentanediol, 1,6-hexanediol, neopentyl glycol, cyclohexanediol, 1,4-cyclohexaned
  • dicarboxylic acids having a molecular weight in the range of 104 to 600 g / mol and / or their anhydrides, such as. Phthalic acid, phthalic anhydride, isophthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, cyclohexanedicarboxylic acid, maleic anhydride, fumaric acid, malonic acid, succinic acid, B-type anhydride, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, dodecanedioic acid.
  • Very particularly preferred dicarboxylic acids are aliphatic dicarboxylic acids having 4-8 C atoms, in particular adipic acid.
  • b3) are acrylic acid and methacrylic acid or mixtures thereof, particularly preferred is acrylic acid.
  • the monohydroxy-functional, (meth) acrylate-containing alcohols described as component B) and oligomers and polymers containing hydroxyl groups and unsaturated groups can be used alone or as mixtures.
  • component C) it is possible with preference to use difunctional amines, di- or tri-functional alcohols and hydroxy-functional polyester alcohols.
  • polyesters for increasing the weight average molecular weight Mw of the polyurethane acrylates are also present in small amounts (preferably ⁇ 5% by weight, more preferably ⁇ 3.5% by weight) of diamines.
  • UV-curable polyurethane dispersions as free-radically crosslinkable infusion agents in the presence of a UV or thermal radical initiator (as part of the infusion formulation) in forced drying / suspending infusion / coating is that the dispersion is radically free at one temperature can be post-cured below the softening temperature of the 3 D printed article. Restrictions such as may occur by pot life in 2K formulations are avoided.
  • component C) polyfunctional alcohols neopentyl glycol, 1,4-butanediol, 1, 4-cyclohexane-dimethanol, 1, 6-hexanediol, 2-ethyl-1, 3-hexanediol, and / or trimethylolpropane used.
  • hydroxy-functional polyester alcohols in component C) are preferably reaction products of phthalic acid, phthalic anhydride, isophthalic acid and / or aliphatic dicarboxylic acids having 4-8 C atoms, in particular adipic acid, and 1,6-hexanediol, 2-ethyl-1, 3-hexanediol, butanediol , Ethylene glycol, di- or triethylene glycol and / or neopentyl glycol used.
  • castor oil as a hydroxy-functional building block.
  • Aliphatic diamines in particular preferably ethylenediamine, 1,6-hexamethylenediamine and / or isophoronediamine, are particularly preferably used as amines in component C)
  • Component D) comprises one or more compounds having at least one isocyanate-reactive group and additionally nonionic, anionic groups or groups capable of forming anionic groups which have a dispensing effect on the polyurethane acrylates.
  • Hydrophilizing groups include anionic groups d1) and / or those which form (for example by salt formation) ionic groups d1) from potentially anionic groups d2), for example sulfonium, phosphonium, carboxylate, sulfonate and / or phosphonate -Groups.
  • suitable isocyanate-reactive groups are hydroxyl and amino groups.
  • Compounds containing potentially anionic groups d2) include compounds such as mono- and dihydroxycarboxylic acids, mono- and diaminocarboxylic acids, mono- and dihydroxysulfonic acids, mono- and diaminosulfonic acids, mono- and dihydroxyphosphonic acids and mono- and diaminophosphonic acids.
  • Preferred compounds containing potentially anionic groups d2) are selected from the group consisting of dimethylolpropionic acid, dimethylolbutyric acid, hydroxypivalic acid, N- (2-aminoethyl) alanine, 2- (2-amino-ethylamino) -ethanesulfonic acid, ethylene-diamine-propyl- or butylsulfonic acid, 1, 2- or 1, 3-propylenediamine ethylsulfonic acid, 3- (cyclohexylamino) -propane-1-sulfonic acid, malic acid, citric acid, glycolic acid, lactic acid, glycine, alanine, taurine, lysine, 3,5-diaminobenzoic acid and an addition product of isophoronediamine (1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, IPDA) and acrylic acid (EP-A 916,647, Example 1).
  • component D) contains as compounds with potentially anionic groups hydroxypivalic acid and / or dimethylolpropionic acid, particularly preferably dimethylolpropionic acid.
  • component D) comprises nonionic compounds which have a dispersing effect on polyurethane acrylates.
  • Nonionic hydrophilic compounds d3) are, for example, monohydric polyalkylene oxide polyether alcohols having a statistical average of 5 to 70, preferably 7 to 55 ethylene oxide units per molecule, as are obtainable in a conventional manner by alkoxylation of suitable starter molecules (eg in Ullmanns Encyclopadie der ischen Chemie, 4. Edition, Volume 19, Verlag Chemie, Weinheim p. 31-38).
  • Suitable starter molecules are, for example, saturated monoalcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, the isomers pentanols, hexanols, octanols and nonanols, n-decanol, n-dodecanol, n-tetradecanol, n Hexadecanol, n-octadecanol, cyclohexanol, the isomeric methylcyclohexanols or hydroxymethylcyclohexane, 3-ethyl-3-hydroxymethyloxetane or tetrahydro for furyl alcohol.
  • saturated monoalcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec
  • Diethylene glycol monoalkyl ethers such as diethylene glycol monobutyl ether
  • unsaturated alcohols such as allyl alcohol, 1,1-dimethylallyl alcohol or oleic alcohol, aromatic alcohols such as phenol, the isomeric cresols or methoxyphenols, araliphatic alcohols such as benzyl alcohol, anisalcohol or cinnamyl alcohol
  • secondary monoamines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, bis (2-ethylhexyl) amine, N-methyl- and N-ethylcyclohexylamine or dicyclohexylamine, and heterocyclic secondary amines such as morpholine, pyrrolidine, piperidine or 1H-pyrazole are also suitable.
  • Preferred starter molecules are saturated monoalcohols and diethylene glycol monoalkyl ethers. Particularly preferred is Di ethyl englykolmonobutylether used as a starter molecule.
  • Alkylene oxides which are suitable for the alkoxylation reaction are, in particular, ethylene oxide and propylene oxide, which can be used in any desired order or even as a mixture in the alkoxylation reaction.
  • the polyalkylene oxide polyether alcohols are either pure polyethylene oxide polyethers or mixed polyalkylene oxide polyethers whose alkylene oxide units consist of at least 30 mol%, preferably at least 40 mol%, of ethylene oxide units.
  • Preferred nonionic hydrophilic compounds A4) are monofunctional mixed polyalkylene oxide polyethers which have at least 40 mol% of ethylene oxide and not more than 60 mol% of propylene oxide units.
  • the compounds listed under component D) can also be used in mixtures.
  • component D ' it is possible with preference to use compounds having potentially cationic groups such as, for example, triethanolamine, N-methyldiethanolamine and N, N-dimethylethanolamine. It is of course also possible to use compounds of a cationic nature, for example compounds having ammonium groups which contain further isocyanate-reactive components. Particular preference is given to using N-methyldiethanolamine.
  • ionic hydrophilization and the combination of ionic and nonionic hydrophilization are preferred over purely nonionic hydrophilization.
  • Component E) contains polyisocyanates selected from the group of aromatic, araliphatic, aliphatic or cycloaliphatic polyisocyanates or mixtures of such polyisocyanates having at least 2 isocyanate groups per molecule.
  • Suitable polyisocyanates are, for example, 1,3-cyclohexanediisocyanate, 1-methyl-2,4-diisocyanato-cyclohexane, 1-methyl-2,6-diisocyanato-cyclohexane, tetramethylene diisocyanate, 4,4'-diisocyanatodiphenylmethane, 2,4'-diisocyanato-cyclohexane.
  • TXDI 1, 3 -Bis (1-isocyanato-1 - methylethyl) benzene
  • TXDI 4-isocyanatomethyl-l, 8-octane diisocyanate (triisocyanatononane, TIN)
  • TIN triisocyanatononane
  • EP-A 928 799 homologs or oligomers of these enumerated Polyisocyanates with biuret, carbodiimide. Isocyanurate, allophanate, iminooxadiazinedione and / or uretdione groups, and mixtures thereof.
  • 1,6-hexamethylene diisocyanate 1-isocyanato-3,3,5-trimethyl-5-isocyanato-methylcyclohexane (isophorone diisocyanate or IPDI) and 4,4'-diisocyanato-dicyclohexylmethane and also homologs or oligomers of hexamethylene diisocyanate, Isocyanato-3, 3, 5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate or IPDI) and 4,4'-diisocyanatodicyclohexylmethane with biuret, carbodiimide, isocyanurate, allophanate, imino-oxadiazinedione and / or uretdione groups and their mixtures.
  • the listed under component E) compounds can be used alone or in mixtures.
  • the acids mentioned under component D) are optionally at by reaction with neutralization amines (component F), typically, but not exclusively tertiary amines, preferably triethylamine, ethyldiisopropylamine, dimethylcyclohexylamine, dimethylethanolamine, methyldiethanolamine, triethanolamine, diethanolamine, N-butyldiethanolamine, ammonia and / or N-ethylmorpholine converted into the corresponding salts.
  • the degree of neutralization is preferably between 50 and 125%.
  • the bases mentioned under component D ') are converted by reaction with neutralizing agents F), such as.
  • neutralizing agents F such as.
  • inorganic acids such as hydrochloric acid, phosphoric acid and / or sulfuric acid
  • organic acids such as formic acid, acetic acid, lactic acid, methane, ethane and / or p-toluenesulfonic acid, converted into the corresponding salts.
  • acetic acid, lactic acid and phosphoric acid is particularly preferred.
  • lactic acid is preferably between 50 and 1 25%.
  • catalysts for accelerating urethane formation.
  • catalysts for this purpose are, for example, tin octoate, tin dioctoate, zinc dioctoate, dibutyltin dilaurate, dimethylbis [(1-oxoneodecyl) oxy] stannane,
  • Dimethyl tin dicarboxylate, zirconium bis (ethyl hexanoate), zirconium acetylacetonate or tertiary amines such as 1,4-diazabicyclo [2.2.2] octane, diazabicyclononane, diazabicycloundecane, 1,1,3,3-tetramethyl-guanidine, 1, 3,4,6,7,8-hexahydro-1-methyl-2H-pyrimido (1,2-a) pyrimidine.
  • tin-free suitable catalysts used for example on bismuth or zirconium base.
  • additives may optionally be used.
  • These may be, for example, conventional additives in the field of coating technology, such as solvents, plasticizers, leveling agents, defoaming agents, stabilizers or adhesion promoters.
  • leveling agent whether surface active compounds such as e.g. Polydimethylsiloxanes are used. It may also be advantageous to simultaneously use several additives of one type. Of course, it may also be beneficial to use several additives of several types.
  • Component A) and optionally components B) and (ii) are used in amounts such that the content of radiation-curable double bonds is between 0.5 and 6.0, preferably between 1.0 and 5.0, particularly preferably between 1.4 and 3.0 mol / kg of non-aqueous constituents of the dispersion.
  • the abovementioned polyurethane dispersion contains a further component, which is a reactive diluent which has at least one free-radically polymerizable group and is at most partially bonded to the polyurethane acrylate via optionally available, incorporable OH groups, otherwise preferably present as an unbound monomer.
  • a reactive diluent which has at least one free-radically polymerizable group and is at most partially bonded to the polyurethane acrylate via optionally available, incorporable OH groups, otherwise preferably present as an unbound monomer.
  • component A) (polyepoxy acrylates) is present as radiation-curable constituent.
  • component A) is then preferably selected from aromatic or aliphatic polyepoxy (meth) acrylates, polyester (meth) acrylates, polyepoxy (meth) acrylates, mono- or dihydroxy-functional (meth) acrylate-containing compounds or mixtures thereof, preferably from polyepoxy (meth) acrylates, particularly preferably from aromatic polyepoxy (meth) acrylates.
  • (Meth) acrylate in the context of this document refers to corresponding acrylate or methacrylate functions or to a mixture of both.
  • the proportion of non-polymer-bonded radiation-curable compounds ⁇ 30 wt .-% based on the solids content of the polyurethane acrylate produced, more preferably ⁇ 20 wt .-%, most preferably ⁇ 10 wt.% Where the non-polymer-bonded radiation-curable compounds in particular as acrylates with two or more CC double bonds.
  • the proportion of isocyanate group-containing compounds is> 10% by weight, based on the solids content of the polyurethane acrylate produced, more preferably>
  • Polymer-bonded radiation-curable groups more preferably, polyurethane (meth) acrylates, polyester (meth) acrylates, polyepoxy (meth) acrylates, polyether (meth) acrylates, particularly preferably polyepoxy (meth) acrylates and / or
  • Polymer-bonded radiation-curable groups by reacting one or more compounds mono- or dihydroxy-functional, (meth) acrylate-containing alcohols with compounds having at least one isocyanate-reactive group, particularly preferred are aliphatic compounds and high proportion of compounds of component E), preferably> 10%, more preferably> 20% as the sum of all NCO-containing feed substances.
  • the polyether chains are linked to at least 60 mol% via allophanate groups with two polyisocyanate molecules each composed of at least two diisocyanates.
  • A) a polyisocyanate component of (average) NCO functionality of 2.0 to 5.0, containing aliphatic, cycloaliphatic, araliphatic and / or aromatic bound isocyanate groups (calculated as NCO, molecular weight 42) of 8.0 to 27.0 wt .-% and a content of monomeric diisocyanates of less than 1 wt .-% with
  • This component A) to be used in the preparation of the water-dispersible polyisocyanates has an (average) NCO functionality of from 2.0 to 5.0, preferably from 2.3 to 4.5, a content of isocyanate groups of from 8.0 to 27, 0 wt .-%, preferably 14.0 to 24.0 wt .-% and a content of monomeric diisocyanates of less than 1 wt .-%, preferably less than 0.5 wt .-% to. It comprises at least one organic polyisocyanate having aliphatically, cycloaliphatically, araliphatically and / or aromatically bound isocyanate groups.
  • the polyisocyanates or polyisocyanate mixtures of component A) are any polyisocyanates prepared by modifying simple aliphatic, cycloaliphatic, araliphatic and / or aromatic diisocyanates and containing at least two diisocyanates with uretdione, isocyanurate, allophanate, biuret, Iminooxadiazinedione and / or oxadiazinetrione structure.
  • Suitable diisocyanates for the preparation of such polyisocyanates are any by phosgenation or by phosgene-free processes, for example by thermal urethane cleavage, accessible diisocyanates of Mol ekulargewi chtsb erei ches 140 to 400 with aliphatic, cycloaliphatic, araliphatic and / or aromatically bound isocyanate groups such.
  • the starting components A) are preferably polyisocyanates or polyisocyanate mixtures of the type mentioned with exclusively aliphatically and / or cycloaliphatically bonded isocyanate groups. Very particularly preferred starting components A) are polyisocyanates or polyisocyanate mixtures with isocyanurate structure based on II DI. IPDI and / or 4,4'-diisocyanatodicyclohexylmethane.
  • This component B) is monovalent, on average 5 to 35, preferably 7 to 30 ethylene oxide units per molecule having Polyalkylenoxidpolyetheralkohole as they are accessible in a conventional manner by alkoxylation of suitable starter molecules or any mixtures of such polyether.
  • starter molecules for preparing these polyether alcohols B) used are: saturated monoalcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, the isomeric pentanols, hexanols, octanols and nonanols; Decanol, n-dodecanol, n-tetradecanol, n-hexadecanol, n-octadecanol, cyclohexanol, the isomeric methylcyclohexanols or hydroxymethylcyclohexane, 3-ethyl-3-hydroxymethyloxetane or tetrahydrofurfuryl alcohol; unsaturated alcohols such as allyl alcohol, 1, 1-dimethyl-allyl alcohol or oleic alcohol, aromatic alcohols such as phenol, the isomeric cre
  • Preferred starter molecules are saturated monoalcohols having up to 4 carbon atoms. Most preferably, methanol is used as a starter molecule.
  • Alkylene oxides which are suitable for the alkoxylation reaction are, in particular, ethylene oxide and propylene oxide, which can be used in any desired order or even as a mixture in the alkoxylation reaction.
  • polyalkylene oxide polyether alcohols B) are either pure polyethylene oxide polyethers or mixed polyalkylene oxide polyethers whose alkylene oxide units consist of at least 30 mol%, preferably at least 40 mol%, of ethylene oxide units.
  • Preferred such starting components B) are pure
  • Polyethylenglycolmonomethyletheralkohole having on average 7 to 30, most preferably 7 to 25 ethylene oxide units.
  • minor amounts of further isocyanate-reactive compounds with anionic or cationic groups for example with carboxylate, sulfonate or ammonium groups, may also be used as hydrophilic synthesis components.
  • the starting components A) and B) at temperatures of 40 to 180 ° C, preferably 50 to 150 ° C, while maintaining an NCO / OH equivalent ratio of 6: 1 to 400: 1, preferably from 8: 1 to 140: 1, reacted with one another such that at least 60 mol%, preferably at least 80 mol%, particularly preferably at least 90 mol% of the urethane groups primarily formed by NCO / OH reaction react further to form allophanate groups.
  • suitable catalysts may optionally be used. These are the customary known allophanatization catalysts, for example metal carboxylates, metal chelates or tertiary amines. Suitable allophanatization catalysts are in particular zinc compounds, such as. Zinc (II) stearate, zinc (II) n-octanoate, zinc (II) 2-ethyl-1-hexanoate, zinc (II) naphthenate or zinc (II) acetylacetonate, Tin compounds, such as.
  • Trifluoroacetic acid sulfuric acid, hydrogen chloride, hydrogen bromide, phosphoric acid or perchloric acid, or any mixtures of these catalysts.
  • the course of the reaction can in this synthesis by z. B. titrimetric determination of the NCO content be followed.
  • the reaction is stopped. This can be done in purely thermal reaction, for example, by cooling the reaction mixture to room temperature temp.
  • suitable catalyst poisons such as acid chlorides such as benzoyl chloride or I sophthaloyldi chloride.
  • the proportions of the starting components in the context of the statements made are selected so that the resulting polyisocyanate mixtures correspond to the statements made above under a) to c), wherein a) the average NCO functionality preferably 2.3 to 9.9, more preferably 2.8 to 5.8, b) the NCO content preferably 6.0 to 22.5 wt .-%, particularly preferably 8.5 to 21.5 wt. % and c) the content of ethylene oxide units bound within polyether chains is preferably from 5 to 40% by weight, particularly preferably from 7 to 25% by weight.
  • the statements made with regard to the NCO functionality of the process products obtained from the synthesis are based on the value calculated from the type and functionality of the starting components of the formula lets determine in which x the proportion of urethane groups reacted in the process according to the invention to form allophanate groups.
  • the functionality fco of the starting polyisocyanates A) can be calculated from the NCO content and the molecular weight determined, for example, by gel permeation chromatography (GPC) or steam pressure osmosis.
  • sections of the article which are contacted with the preparation have a porosity ⁇ of> 0.01 to ⁇ 0.6.
  • the porosity ⁇ is expressed as:
  • ⁇ 1 - (p / po)
  • p denotes the density of the volume associated with the portions of the article which are contacted with the formulation
  • po denotes the true density of the building material.
  • the porosity is preferably ⁇ > 0.1 to ⁇ 0.5 and more preferably> 0.2 to ⁇ 0.4. With such porous volumes, the aqueous preparation can also penetrate to a greater extent in the interior of the volume and also lead there to improve the density and the mechanical properties of the article. In powder sintering processes, by deliberately reducing the power of the laser used for sintering, the porosity of the 3D printed article can be controlled within certain limits.
  • the production of the article by means of the additive manufacturing method comprises the steps:
  • the article is a powder sintering or powder melting process. If the number of repetitions for application and irradiation is sufficiently low, it is also possible to speak of a two-dimensional object that is to be set up. Such a two-dimensional object can also be characterized as a coating. For example, for its construction,> 2 to ⁇ 20 recoveries for application and irradiation can be performed.
  • the particles have a particle diameter of ⁇ 0.25 mm, preferably ⁇ 0.2 mm, particularly preferably ⁇ 0.15 mm.
  • the energy source for joining the particles may be electromagnetic energy, such as UV to IR light. Also conceivable is an electron beam.
  • the bonding of the particles in the irradiated part of the particle layer is usually carried out by (partial) melting of a (partly) crystalline material and bonding of the material on cooling. But it is also possible that other Ge Staltumwandlened the particles such as a glass transition, that is, the heating of the material to a temperature above the Glasüb ergangst emp ERIC, cause a compound of the particles of the particles with each other.
  • the application of energy to a selected part of the layer, corresponding to a cross-section of the article so that the particles in the selected part are joined comprises the following step:
  • the energy beam for connecting the particles may be a beam of electromagnetic energy, such as a "light beam” of UV to IR light,
  • the energy beam is a laser beam, particularly preferably with a wavelength between 600 nm and 15 ⁇ m
  • a laser beam is also conceivable.
  • the action of energy comprises one selected portion of the layer, corresponding to a cross-section of the article, so that the particles are joined in the selected part, the following steps:
  • a liquid containing an IR absorber by means of Inkj et- method are applied to the layer.
  • the irradiation of the layer leads to a selective heating of those particles which are in contact with the liquid together with the IR absorber.
  • a connection of the particles can be achieved.
  • a second liquid can be used which is complementary to the energy absorbing liquid in terms of behavior with respect to the energy used. In areas where the second liquid is applied, the energy used is not absorbed, but reflected. The areas under the second liquid are thus shaded. In this way, the selectivity to be melted and not melted areas of the layer can be increased.
  • the production of the article by means of the additive manufacturing method comprises the steps:
  • This embodiment is a fused deposition or fused deposition modeling (FDM) process.
  • FDM fused deposition modeling
  • Is the number of repeats sufficient for application low, can also be spoken of a two-dimensional object to be built.
  • Such a two-dimensional object could also be characterized as a coating.
  • the individual filaments which are applied can have a diameter of> 30 ⁇ m to ⁇ 2000 ⁇ m, preferably> 40 ⁇ m to ⁇ 1000 ⁇ m and particularly preferably> 50 ⁇ m to ⁇ 500 ⁇ m.
  • the first step of this embodiment of the method relates to the construction of the first layer on a carrier. Subsequently, the second step is carried out as long as further layers are applied to previously applied layers of the building material until the desired final result in the form of the article is obtained.
  • the at least partially melted build material bonds to preexisting layers of the material to build a structure in the z direction.
  • the build-up material comprises a thermoplastic polyurethane elastomer which has a melting range (DSC, differential scanning calorimetry, second heating at a heating rate of 5 K / min) of> 20 ° C. to ⁇ 240 ° C.
  • a Shore hardness according to DI I SO 7619-1 of> 40 A to ⁇ 85 D preferably> 50 Shore Abis ⁇ 80 Shore D, more preferably> 60 Shore A to ⁇ 75 Shore D.
  • the material is subjected to the following temperature cycle: 1 minute at minus 60 ° C, then heating to 240 ° C at 20 Kelvin / minute, then cooling to minus 60 ° C at 5 Kelvin / minute, then 1 minute at minus 60 ° C, then heating to 240 ° C at 20 Kelvin / minute.
  • the build-up material comprises a thermoplastic polyurethane elastomer which has a melting range (DSC, Differential Scanning Calorimetry, second heating at a heating rate of 5 K / min) of> 20 ° C. to ⁇ 240 ° C.
  • DSC Differential Scanning Calorimetry, second heating at a heating rate of 5 K / min
  • the material is subjected to the following temperature cycle: 1 minute at -60 ° C, then heating to 220 ° C at 20 Kelvin / minute, then cooling to -60 ° C at 5 Kelvin / minute, then 1 minute at minus 60 ° C, then heating to 220 ° C with 20 Kelvin / minute.
  • thermoplastic elastomer preferably a thermoplastic polyurethane elastomer
  • the melting behavior is determined by changing the MVR (melt volume rate) according to ISO 1133 at 5 minutes preheating time and 10 kg depending on the temperature.
  • MVR melt volume rate
  • a melting behavior applies if the MVR x has an initial value of 5 to 15 cm 3/10 min at an initial temperature T and temp erature increase of 20 ° C to T x + 2o by no more than 90 cm 3 / 10 min rises.
  • the build-up material comprises a thermoplastic polyurethane elastomer which is obtainable from the reaction of the components: a) at least one organic diisocyanate b) at least one compound having a number average molecular weight (M n ) of> having isocyanate-reactive groups 500 g / mol to ⁇ 6000 g / mol and a number-average functionality of the total of the components under b) of> 1.8 to ⁇ 2.5 c) at least one chain extender having a molecular weight (Mn) of 60-450 g / mol and a number average Functionality of the entirety of the chain extenders under c) from 1.8 to 2.5.
  • a thermoplastic polyurethane elastomer which is obtainable from the reaction of the components: a) at least one organic diisocyanate b) at least one compound having a number average molecular weight (M n ) of> having isocyanate-reactive groups 500 g / mol to ⁇ 6000
  • thermoplastic polyurethane elastomer TPU
  • anocyanate component under a): aliphatic diisocyanates such as ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cycloaliphatic Diisocyanates such as isophorone diisocyanate, 1,4-cyclohexane diisocyanate, 1-methyl-2,4-cyclohexane diisocyanate and 1-methyl-2,6-cyclohexane diisocyanate and the corresponding isomer mixtures, 4,4'-dicyclohexylmethane diisocyanate, 2,4'-dicyclohexylmethane diisocyanate and 2, 2 '
  • Dicyclohexylmethandiisocyanat and the corresponding isomer mixtures also aromatic diisocyanates such as 2,4-tolylene diisocyanate, mixtures of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate.
  • aromatic diisocyanates such as 2,4-tolylene diisocyanate, mixtures of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate.
  • aromatic diisocyanates such as 2,4-tolylene diisocyanate, mixtures of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate.
  • the diisocyanates mentioned can be used individually or in the form of mixtures with one another.
  • polyisocyanates can also be used together with up to 15 mol% (calculated on the total diisocyanate) of a polyisocyanate, but at most so much polyisocyanate may be added that a still thermoplastically processable product is formed.
  • polyisocyanates are triphenylmethane-4,4 ', 4 "-triisocyanate and polyphenyl-polymethylene-polyisocyanates.
  • Examples of longer-chain isocyanate-reactive compounds under b) are those having on average at least 1.8 to 3.0 Zerewitinoff-active hydrogen atoms and a number-average molecular weight of 500 to 10,000 g / mol.
  • amino groups containing thiol groups or compounds containing carboxyl groups in particular two to three, preferably two hydroxyl groups having compounds, especially those with number average molecular weights Mn from 500 to 6000 g / mol, particularly preferably those having a number average molecular weight Mn from 600 to 4000 g / mol For example, hydroxyl-containing polyester polyols, polyether polyols, polycarbonate polyols and polyester polyamides.
  • Suitable polyester diols can be prepared by reacting one or more alkylene oxides having 2 to 4 carbon atoms in the alkylene radical with a starter molecule which contains two active hydrogen sto ffatome bound.
  • suitable alkylene oxides are: ethylene oxide, 1,2-propylene oxide, epichlorohydrin and 1,2-butylene oxide and 2,3-butylene oxide.
  • Preferably used are ethylene oxide, propylene oxide and mixtures of 1, 2-propylene oxide and ethylene oxide.
  • the alkylene oxides can be used individually, alternately in succession or as mixtures.
  • Suitable starter molecules include, for example, water, amino alcohols, such as N-alkyl-diethanolamine, for example N-methyl-diethanolamine and diols, such as ethylene glycol, 1,3-propylene glycol, 1,4-butanediol and 1,6-hexanediol.
  • amino alcohols such as N-alkyl-diethanolamine, for example N-methyl-diethanolamine
  • diols such as ethylene glycol, 1,3-propylene glycol, 1,4-butanediol and 1,6-hexanediol.
  • Suitable polyether diols are also the hydroxyl-containing polymerization of tetrahydrofuran. It is also possible to use tri-functional polyethers in proportions of from 0 to 30% by weight, based on the bifunctional polyether diols, but at most in such an amount that a product which is still melt-processible is formed.
  • the substantially linear polyether diols preferably have number average molecular weights n of 500 to 6000 g / mol. They can be used both individually and in the form of mixtures with one another.
  • Suitable polyester diols can be prepared, for example, from di-carboxylic acids having 2 to 12 carbon atoms, preferably 4 to 6 carbon atoms, and polyhydric alcohols. Examples of suitable dicarboxylic acids are: aliphatic dicarboxylic acids, such as succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid and sebacic acid, or aromatic dicarboxylic acids, such as phthalic acid, isophthalic acid and terephthalic acid.
  • the dicarboxylic acids can be used individually or as mixtures, for example in the form of an amber, glutaric and adipic acid mixture.
  • the corresponding di carbon acid derivatives such as carboxylic acid ediester having 1 to 4 carbon atoms in the alcohol radical, carboxylic anhydrides or carboxylic acid chlorides to use.
  • polyhydric alcohols are glycols having 2 to 10, preferably 2 to 6 carbon atoms, for example: Ethylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, 2,2-dimethyl-1,3-propanediol, 1,3-propanediol or dipropylene glycol.
  • the polyhydric alcohols may be used alone or mixed with each other.
  • esters of carbonic acid with the diols mentioned in particular those having 4 to 6 carbon atoms, such as 1, 4-butanediol or 1, 6-hexanediol, condensation products of ⁇ -hydroxy carboxylic acids such as ⁇ -hydroxycaproic acid or polymerization of lactones, for example optionally substituted ⁇ -caprolactone.
  • polyester diols Preferably used as polyester diols are ethanediol polyadipates, 1,4-butanediol polyadipates, ethanediol 1,4-butanediol polyadipates, 1,6-hexanediol neopentyl glycol polyadipates, 1,6-hexanediol 1,4-butanediol polyadipates and polycaprolactones.
  • the polyester diols preferably have number-average molecular weights Mn of 450 to 6000 g / mol and can be used individually or in the form of mixtures with one another.
  • the chain extenders under c) have an average of 1.8 to 3.0 Zerewitinoff-active Wass er sto ffatome and have a molecular weight of 60 to 450 g / mol.
  • these is meant, in addition to amino groups, thiol groups or carboxyl-containing compounds, those having two to three, preferably two hydroxyl groups.
  • the chain extenders used are preferably aliphatic diols having 2 to 14 carbon atoms, such as ethanediol, 1, 2-propanediol, 1,3-propanediol, 1, 4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1, 6 Hexanediol, diethylene glycol and dipropyl englycol.
  • diesters of terephthalic acid with glycols having 2 to 4 carbon atoms for example terephthalic acid bis-ethylene glycol or terephthalic acid bis- 1, 4-butanediol, hydroxyalkyleneth he hydroquinone, eg 1, 4-di (b-hydroxyethyl) - hydroquinone, ethoxylated bisphenols, for example 1,4-di (b-hydroxyethyl) bisphenol A, (cyclo) aliphatic diamines, such as isophoronediamine, ethylenediamine, 1, 2-propylenediamine, 1, 3-propylenediamine, N-methyl-propylene-1 , 3 -diamine, ⁇ , ⁇ '- Dimethyl ethylenediamine and aromatic diamines, such as 2,4-toluenediamine, 2, 6-toluenediamine, 3,5-diethyl-2,4-toluenediamine or 3,5-diethyl-2,
  • Ethanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-di ( ⁇ -hydroxyethyl) hydroquinone or 1,4-di ( ⁇ -hydroxyethyl) bisphenol A are particularly preferably used as chain extenders. It is also possible to use mixtures of the abovementioned chain extenders.
  • triols can be added.
  • Compounds which are monounsaturated with respect to isocyanates can be used under f) in proportions of up to 2% by weight, based on TPU, as so-called chain terminators.
  • Suitable are e.g.
  • Monoamines include butyl and dibutylamine, octylamine, stearylamine, N-methylstearylamine, pyrrolidine, piperidine or cyclohexylamine, monoalcohols such as butanol, 2-ethylhexanol, octanol, dodecanol, stearyl alcohol, the various amyl alcohols, cyclohexanol and ethylene glycol monomethyl ether.
  • the isocyanate-reactive substances should preferably be selected so that their number-average functionality does not significantly exceed two if thermoplastically processable polyurethane elastomers are to be produced. If compounds with higher functionality are used, compounds with a functionality ⁇ 2 should reduce the overall functionality accordingly.
  • the relative amounts of the groups cyanate groups and isocyanate-reactive groups are preferably chosen such that the ratio is 0.9: 1 to 1.2: 1, preferably 0.95: 1 to 1.1: 1.
  • thermoplastic polyurethane elastomers used according to the invention may contain as auxiliary agents and / or additives up to a maximum of 50% by weight, based on the total amount of TPU, of the customary auxiliaries and additives.
  • Typical auxiliaries and additives are catalysts, antiblocking agents, inhibitors, pigments, dyes, flame retardants, stabilizers against aging and weathering, against hydrolysis, light, heat and discoloration, plasticizers, lubricants and mold release agents, fungi static and bacteriostatic substances, reinforcing agents and inorganic and / or organic fillers and mixtures thereof.
  • additives examples include lubricants such as fatty acid esters, metal soaps, fatty acid amides, fatty acid ester amides and silicone compounds, and reinforcing agents such as fibrous reinforcing agents such as inorganic fibers which are produced by the prior art and can also be applied with a sizing agent , Further details of the abovementioned auxiliaries and additives can be found in the specialist literature, for example the monograph by JH Saunders and KC Frisch "High Polymers", Volume XVI, Polyurethanes, Part 1 and 2, Verlag Interscience Publishers 1962 and 1964, the paperback for plastic additives by R. Gumbleter u. H. Müller (Hanser Verlag Kunststoff 1990) or DE-A 29 01 774.
  • lubricants such as fatty acid esters, metal soaps, fatty acid amides, fatty acid ester amides and silicone compounds
  • reinforcing agents such as fibrous reinforcing agents such as inorganic fibers which are produced by the prior art and
  • Suitable catalysts are the tertiary amines known and customary in the art, e.g. Triethylamine, dimethylcyclohexylamine, N-methylmorpholine, ⁇ , ⁇ '-dimethylpiperazine, 2- (dimethylaminoethoxy) ethanol, diazabicyclo [2,2,2] octane and the like and in particular organic metal compounds such as titanic acid esters, iron compounds or tin compounds such as tin diacetate, tin dioctoate, tin dilaurate or the tin dialkyl salts of aliphatic carboxylic acids such as dibutyltin diacetate or dibutyltin dilaurate or the like.
  • organic metal compounds such as titanic acid esters, iron compounds or tin compounds such as tin diacetate, tin dioctoate, tin dilaurate or the tin dialkyl salts of aliphatic carb
  • Preferred catalysts are organic metal compounds, in particular titanic acid esters, iron and tin compounds.
  • the total amount of catalysts in the TPU used is generally about 0 to 5 wt .-%, preferably 0 to 2 wt .-%, based on the total amount of TPU.
  • the build-up material comprises a thermoplastic polyurethane elastomer which has a melting range (DSC, differential scanning calorimetry, 2. heating at a heating rate of 5 K / min.) Of> 20 ° C. to ⁇ 100 ° C. and Amount of complex viscosity ⁇ ⁇ ⁇ (determined by viscometry measurement in the melt with a plate / plate Oszillationsscherviskosimeter at 100 ° C and an angular frequency of l / 's) of> 10 Pas to ⁇ 1000000 Pas.
  • a melting range DSC, differential scanning calorimetry, 2. heating at a heating rate of 5 K / min.
  • Amount of complex viscosity ⁇ ⁇ ⁇ determined by viscometry measurement in the melt with a plate / plate Oszillationsscherviskosimeter at 100 ° C and an angular frequency of l / 's
  • This thermoplastic elastomer has a melting range of from> 20 ° C to ⁇ 100 ° C, preferably from> 25 ° C to ⁇ 90 ° C, and more preferably from> 30 ° C to ⁇ 80 ° C.
  • the material is subjected to the following temperature cycle: 1 minute at -60 ° C, then heating to 200 ° C at 5 Kelvin / minute, then cooling to -60 ° C at 5 Kelvin / minute, then 1 minute at -60 ° C, then heat to 200 ° C with 5 Kelvin / minute.
  • Temp eraturintervall between the beginning of the melting process and the end of the melting process can be determined according to the above DSC protocol, ⁇ 20 ° C, preferably ⁇ 10 ° C and more preferably ⁇ 5 ° C.
  • This thermoplastic elastomer further has an amount of complex viscosity ⁇ ⁇ ⁇ (determined by melt viscometry measurement with a plate / plate oscillation viscosimeter according to I SO 6721-10: 2015-09 at 100 ° C and an angular frequency of 1 / s) of > 10 Pas to ⁇ 1000000 Pas.
  • the amount of the complex viscosity ⁇ ⁇ * ⁇ describes the ratio of the viscoelastic moduli G ' (Storage modulus) and G "(loss modulus) to the excitation frequency ⁇ in a dynamic mechanical material analysis:
  • the building material comprises a thermoplastic polyurethane elastomer obtainable from the reaction of a polyisocyanate component and a polyol component, wherein the polyol component comprises a polyester polyol having a pour point (ASTM D5985) of> 25 ° C.
  • this polyurethane diols of the molecular weight range of> 62 to ⁇ 600 g / mol can be used as a chain extender.
  • This polyisocyanate component may comprise a symmetrical polyisocyanate and / or a nonsymmetric polyisocyanate.
  • symmetrical polyisocyanates are 4,4'-MDI and HDI.
  • non-symmetrical polyisocyanates the steric environment of one NCO group in the molecule is different from the steric environment of another NCO group.
  • An isocyanate group then reacts more rapidly with isocyanate-reactive groups, for example OH groups, while the remaining isocyanate group is less reactive.
  • isocyanate-reactive groups for example OH groups
  • non-symmetrical polyisocyanates are selected from the group comprising: 2,2,4-trimethyl-hexamethylene diisocyanate, ethylethylene diisocyanate, nonsymmetric isomers of dicyclohexylmethane diisocyanate ⁇ H r - DI), non-symmetrical isomers of 1,4-diisocyanatocyclohexane, non-symmetric Isomers of 1,3-diisocyanatocyclohexane, non-symmetrical isomers of 1,2-diisocyanatocyclohexane, non-symmetrical isomers of 1,3-diisocyanatocyclopentane, non-symmetrical isomers of 1,2-diisocyanato clopentane, non-symmetrical isomers of 1, 2-diisocyanatocyclobutane, 1-isocyanatomethyl-3-isocyanato-1, 5,5-trimethylcyclohexane (isophorone
  • This polyol component comprises a polyester polyol having a pour point (No Flow Point, ASTM D5985) of> 25 ° C, preferably> 35 ° C, more preferably> 35 ° C to ⁇ 55 ° C.
  • a measuring vessel is placed in a slow rotation (0.1 rpm) with the sample.
  • a flexibly mounted measuring head dips into the sample and is moved on reaching the pour point by the sudden increase in viscosity from its position, the resulting tilting movement triggers a sensor.
  • polyester polyols which may have such a pour point are reaction products of phthalic acid, phthalic anhydride or symmetrical ⁇ , ⁇ - ⁇ to Cio- di-carboxylic acids with one or more C2 to Oo-diols. They preferably have a number average molecular weight M n of> 400 g / mol to ⁇ 6000 g / mol.
  • Particularly suitable diols are monoethylene glycol, 1,4-butanediol, 1,6-hexanediol and neopentyl glycol.
  • Preferred polyester polyols are given below with indication of their acid and diol components: adipic acid + monoethylene glycol; Adipic acid + monoethylene glycol + 1, 4-butanediol; Adipic acid + 1, 4-butanediol; Adipic acid + 1, 6-hexanediol + neopentyl glycol; Adipic acid + 1,6-hexanediol; Adipic acid + 1, 4-butanediol + 1,6-hexanediol; Phthalic acid (anhydride) + monoethylene glycol + trimethylolpropane; Phthalic acid (anhydride) + monoethylene glycol.
  • Preferred polyurethanes are obtained from a mixture containing I DI and HDI as the polyisocyanate component and a polyol component containing a preferred polyester polyol mentioned above. Particularly preferred is the combination of a mixture containing I DI and HDI as a polyisocyanate component with a polyester polyol of adipic acid + 1, 4-butanediol + 1,6-hexanediol to build up the polyurethanes.
  • polyester polyols have an OH number (DIN 53240) of> 25 to ⁇ 170 mg KOH / g and / or a viscosity (75 ° C, DIN 5 1550) of> 50 to ⁇ 5000 mPas.
  • a polyurethane obtainable from the reaction of a polyisocyanate component and a polyol component, the polyisocyanate component comprising an HDI and I DI and wherein the polyol component comprises a polyester polyol resulting from the reaction of a reaction mixture comprising adipic acid and 1,6-hexanediol and 1, 4- Butanediol with a molar ratio of these diols of> 1: 4 to ⁇ 4: 1 is available and which has a number average molecular weight M n (GPC, against polystyrene standards) of> 4000 g / mol to ⁇ 6000 g / mol.
  • M n number average molecular weight
  • Such a polyurethane may have an amount of complex viscosity ⁇ ⁇ ⁇ (determined by melt viscometry measurement with a plate / plate oscillation viscosimeter according to I SO 6721-10: 2015-09 at 100 ° C and an angular frequency of 1 / s) of> 4000 Pas to have ⁇ 160000 Pas.
  • Another example of a suitable polyurethane is:
  • component a) consists of 100% of a polyester diol in the molecular weight range 4000 to 6000, in their preparation as a diol mixture, a mixture of 1, 4-dihydroxybutane and 1, 6-dihydroxyhexane in a molar ratio of 7: 3 to 1: 2 has been used.
  • polyester polyurethanes mentioned under 1 is further preferred that the component c) IPDI and further HDI contains.
  • alkanediols selected from the group consisting of: 1, 2-dihydroxyethane, 1, 3 -dihydroxypropane, 1, 4-dihydroxybutane, 1, 5- Dihydroxypentane, 1, 6-dihydroxyhexane or a combination of at least two thereof, in an amount of up to 200 hydroxyl equivalent percent, based on the component a), have been used.
  • thermoplastic elastomer after heating to 100 ° C and cooling to 20 ° C at a cooling rate of 4 ° C / min in a temperature range of 25 ° C to 40 ° C for> 1 minute (preferably> 1 minute to ⁇ 30 minutes, more preferably> 10 minutes to ⁇ 1 5 minutes), a storage modulus G '(determined at the prevailing temperature with a plate / plate Oscilationsviskosimeter according to ISO 6721 -10: 2015-09 at an angular frequency of 1 / s) of> 100 kPa to ⁇ 1 MPa and after cooling to 20 ° C and storage for 20 minutes a storage modulus G '(determined at 20 ° C with a plate / plate Oscillatory viscometer according to ISO 6721 -10: 2015-09 at an angular frequency of 1 / s) of> 10 MPa.
  • a building material comprising polyurethane which is obtainable from the reaction of a polyisocyanate component and a polyol component, wherein the
  • Polyisocyanate component comprises a H DI and IPDI and wherein the polyol component comprises a polyester polyol, which from the reaction of a reaction mixture comprising adipic acid and 1,6-hexanediol and 1, 4-butanediol with a molar ratio of these diols of> 1: 4 to ⁇ 4: 1 is available and which has a number average molecular weight M n (GPC, against polystyrene standards) of> 4000 g / mol to ⁇ 6000 g / mol; anionic aliphatic polyester-polyurethane dispersion.
  • M n number average molecular weight
  • a building material comprising polyurethane which is obtainable from the reaction of a polyisocyanate component and a polyol component, wherein the
  • Polyisocyanate component comprises an MDI (preferably 4,4'-MDI) and wherein the polyol component comprises a polyesterpolyol, which consists of the reaction of a reaction mixture comprising adipic acid and 1, 6-hexanediol and 1, 4-butanediol with a molar ratio of these diols of> 1: 4 to ⁇ 4: 1 and which has a number average molecular weight M n (GPC, against polystyrene standards) of> 4000 g / mol to ⁇ 6000 g / mol; anionic aliphatic polyester-polyurethane dispersion.
  • MDI preferably 4,4'-MDI
  • the present invention further relates to an at least partially coated article obtained by a method according to the invention.
  • the invention is further illustrated by the following examples, but is not limited thereto.
  • Diaminosulphonate NI L-ILCIL-NH-CILC i L-SO ⁇ Na (45% in water)
  • Desmophen 2020 / C2200 polycarbonate polyol, OH number 56 mg KOH / g, number average
  • Po KT H F 2000 polytetramethylene glycol polyol, OH number 56 mg KOH / g, number average molecular weight 2000 g / mol (BASF AG,
  • P l vT HF 1000 polytetramethylene glycol polyol, oil number 112 mg KOH / g, number average molecular weight 1000 g / mol (BASF AG, Ludwigshafen, DE)
  • Polyether LB 25 monofunctional ethylene oxide / propylene oxide based polyether, number average molecular weight 2250 g / mol, OH number 25 mg KOH / g (Covestro AG, Leverkusen, DE)
  • Example 1 Example 1 :
  • the finished prepolymer was dissolved with 4830 g of acetone while cooled to 50 ° C and then a solution of 25.1 g of ethylenediamine, 116.5 g of isophoronediamine, 61.7 g of diaminosulfonate and 1030 g of water was added within 10 min. The stirring time was 10 min. Then was dispersed by adding 1250 g of water. This was followed by removal of the solvent by distillation in vacuo. The residual content of acetone was less than 1% by weight, based on the finished dispersion.
  • the resulting white dispersion had the following properties:
  • Viscosity (viscometer, 23 ° C): 241 mPas
  • Viscosity 1000 mPas
  • Viscosity 1300 mPas
  • a powdery, ester-based thermoplastic polyurethane was used, as described in Example 1 of WO 2015/197515 Al.
  • polyester diol having a number average molecular weight of about 900 g / mol based on about 56.7 wt .-% adipic acid and about 43.3 wt .-% 1,4-butanediol and about !
  • the TPU obtained had the following properties: melting range (DSC, Differential Scanning Calorimetry, second heating with heating rate 5 K / min) from> 20 ° C to ⁇ 200 ° C, Shore A hardness according to DIN ISO 7619-1 from> 40 A to ⁇ 85 D, at a temperature T a melt volume rate (melt volume rate MVR) according to I SO 1133 (10 kg) 5 to 15 cm 3/10 min and a change in the melt volume rate (10 kg) with an increase in this temperature T is 20 ° C of ⁇ 90 cm 3 / l 0 min.
  • an S2 specimen was prepared by a powder laser sintering method (SLS).
  • the S2 sample body obtained was immersed in an aqueous polyurethane dispersion with the name Impranil DI.N W50 (Covestro AG, Leverkusen, DE), an anionic aliphatic polyester-polyurethane dispersion, for 10 minutes and then dried at room temperature to constant weight.
  • Impranil DI.N W50 Covestro AG, Leverkusen, DE
  • the specimen was evaluated before and after the coating with the polyurethane dispersion in terms of its haptic properties on a scale of 1 to 5 points, with a score of 1 point very unpleasant haptic properties and a rating of 5 points very pleasant haptic properties.
  • the specimen before coating was scored 2 points and after coating 4 points.
  • the specimens thus obtained with a porosity ⁇ of about 0.3 were immersed in various aqueous dispersions for 10 minutes at room temperature, then drained for 15 minutes, then annealed for 15 minutes at 70 ° C and a further 3 minutes at 100 ° C in a convection oven and after a further 3 days storage at room temperature in the tensile test according to DIN 53504 tested.
  • the modulus of elasticity at 50% elongation and the elongation at break and the breaking stress were tested.
  • the printer used was a Prusa i3 MK2 with a nozzle of 0.4 mm and a temperature of 255 ° C.
  • the printing parameters were: extrusion die diameter 0.4 mm, layer height 0.2 mm, printing speed 40 mm / s, infill 1 00%, extrusion temperature 255 ° C., pressure bed temperature 100 ° C.
  • ABS sample bodies in S2 bar form obtained in this way were immersed in various aqueous dispersions for 10 minutes at room temperature, then drained for 15 minutes, then annealed at 70 ° C. for 15 minutes and at 100 ° C. for a further 3 minutes in a circulation cuvette and after a further 3 days of storage at room temperature tested in the tensile test according to DI 53504.
  • the modulus of elasticity at 50% elongation and the elongation at break and the breaking stress were tested.
  • the specimen was evaluated before and after the coating with the polyurethane dispersion in terms of its haptic properties on a scale of 1 to 5 points, with a score of 1 point very unpleasant haptic properties and a rating of 5 points very pleasant haptic properties.
  • the specimen before coating was scored 3 points and after coating 4 points.

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  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Optics & Photonics (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Laminated Bodies (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne un procédé pour fabriquer un objet au moins en partie recouvert, comprenant l'étape de fabrication de l'objet au moyen d'un procédé de fabrication additionnel à partir d'un matériau constitutif, ledit matériau de construction comprenant un matériau de polyuréthane thermoplastique. Le procédé comprend en outre, après la fabrication, l'étape consistant à mettre au moins en partie en contact l'objet avec une préparation qui est choisie parmi : - une dispersion de polyuréthane aqueuse, - une dispersion aqueuse d'un polymère présentant des groupes OH, cette dispersion contenant en outre un composé présentant des groupes NCO, - une préparation aqueuse d'un composé contenant des groupes NCO, cette préparation ne contenant pas de polymères présentant des groupes OH ou de combinaison d'au moins deux de ceux-ci. L'invention concerne en outre un objet au moins en partie recouvert, qui a été obtenu par un procédé selon l'invention.
EP17809230.0A 2016-11-25 2017-11-22 Procédé de fabrication d'un objet revêtu au moins partiellement Active EP3545025B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP16200725 2016-11-25
PCT/EP2017/080037 WO2018095967A1 (fr) 2016-11-25 2017-11-22 Procédé pour fabriquer un objet au moins en partie recouvert

Publications (2)

Publication Number Publication Date
EP3545025A1 true EP3545025A1 (fr) 2019-10-02
EP3545025B1 EP3545025B1 (fr) 2022-10-12

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Application Number Title Priority Date Filing Date
EP17809230.0A Active EP3545025B1 (fr) 2016-11-25 2017-11-22 Procédé de fabrication d'un objet revêtu au moins partiellement

Country Status (6)

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US (1) US11981095B2 (fr)
EP (1) EP3545025B1 (fr)
JP (1) JP7061122B2 (fr)
KR (1) KR102477958B1 (fr)
CN (1) CN109963898B (fr)
WO (1) WO2018095967A1 (fr)

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WO2019241227A2 (fr) * 2018-06-11 2019-12-19 Tepha, Inc. Procédés d'impression 3d de poly-4-hydroxybutyrate et de copolymères
EP3666810B1 (fr) 2018-12-13 2023-02-08 Evonik Operations GmbH Agent d'hydrophilisation pauvre en eau et son utilisation dans des dispersions aqueuses
KR20210122823A (ko) * 2019-02-01 2021-10-12 바스프 에스이 폴리우레탄 및 이를 포함하는 uv-수분 이중 경화 pu 반응성 핫멜트
CN110539491A (zh) * 2019-09-09 2019-12-06 安徽卓锐三维科技有限公司 一种基于sls三维打印技术的可穿戴产品及其制备方法
WO2021063806A1 (fr) 2019-09-30 2021-04-08 Covestro Intellectual Property Gmbh & Co. Kg Procédé de modification d'un objet imprimé en 3d
US11028217B1 (en) * 2020-03-13 2021-06-08 Biocellection Inc. Thermoplastic polyurethane compositions comprising nitro-substituted polyester diols
TWI747712B (zh) * 2021-01-14 2021-11-21 國立臺灣科技大學 3d列印套組、以及使用其進行3d噴墨列印之方法
EP4330304A1 (fr) 2021-04-26 2024-03-06 Stratasys, Inc. Procédé permettant de produire un objet au moins partiellement revêtu
EP4101872A1 (fr) 2021-06-07 2022-12-14 Covestro Deutschland AG Procédé pour fabriquer un objet au moins en partie revêtu

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Publication number Publication date
US11981095B2 (en) 2024-05-14
JP7061122B2 (ja) 2022-04-27
KR102477958B1 (ko) 2022-12-19
US20190375153A1 (en) 2019-12-12
KR20190087519A (ko) 2019-07-24
CN109963898A (zh) 2019-07-02
JP2020500969A (ja) 2020-01-16
CN109963898B (zh) 2022-07-05
EP3545025B1 (fr) 2022-10-12
WO2018095967A1 (fr) 2018-05-31

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